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Title: Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet

Abstract

A flowsheet has been proposed to separate neptunium from solutions in H-Canyon Tanks 16.4, 12.5, and 11.7 in the First Cycle solvent extraction banks, in which cerium(IV) (Ce(IV)) serves as an agent to oxidize neptunium to neptunium(VI) (Np(VI)). A SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) spreadsheet model indicates that the proposed flowsheet is a feasible method for separating neptunium and uranium from sulfates, thorium, and other metal impurities. The proposed flowsheet calls for stripping the sulfates, thorium, and other metal impurities into the 1AW stream and extracting and then stripping the neptunium and uranium into the 1BP stream. SASSE predicts that separation of thorium from the other actinides can be accomplished with actinide losses of 0.01% or less. It is assumed that other metal impurities such as iron, aluminum, and fission products will follow the thorium into 1AW. Due to an organic/aqueous distribution coefficient that is close to one, SASSE predicts that plutonium(VI) (Pu(VI)) is split between the A Bank and B Bank aqueous output streams, with 27% going to 1AW and 73% going to 1BP. An extrapolated distribution coefficient based on unvalidated Ce(IV) distribution measurements at a single nitrate concentration and a comparison with thorium(IV) (Th(IV)) distributions indicatesmore » that Ce(IV) could reflux in 1B Bank. If the Ce(IV) distribution coefficient is lower than would be predicted by this single point extrapolation, but still higher than the distribution coefficient for Th(IV), then Ce(IV) would follow Np(VI) and uranium(VI) (U(VI)) into 1BP. The SASSE model was validated using data from a 1964 oxidizing flowsheet for the recovery of Np(VI) in Second Cycle. For the proposed flowsheet to be effective in recovering neptunium, the addition of approximately 0.025 M ceric ammonium nitrate (Ce(NH 4) 2(NO 3) 6) to both the 1AF and 1AS streams is required to stabilize the neptunium in the +6 oxidation state. The cerium added to 1AF and 1AS must remain in the +4 oxidation state to stabilize Np(VI).« less

Authors:
 [1]
  1. Savannah River Site (SRS), Aiken, SC (United States)
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1183724
Report Number(s):
WSRC-TR-2006-00104
DOE Contract Number:
AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English

Citation Formats

Laurinat, J. E. Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet. United States: N. p., 2006. Web. doi:10.2172/1183724.
Laurinat, J. E. Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet. United States. doi:10.2172/1183724.
Laurinat, J. E. Sat . "Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet". United States. doi:10.2172/1183724. https://www.osti.gov/servlets/purl/1183724.
@article{osti_1183724,
title = {Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet},
author = {Laurinat, J. E.},
abstractNote = {A flowsheet has been proposed to separate neptunium from solutions in H-Canyon Tanks 16.4, 12.5, and 11.7 in the First Cycle solvent extraction banks, in which cerium(IV) (Ce(IV)) serves as an agent to oxidize neptunium to neptunium(VI) (Np(VI)). A SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) spreadsheet model indicates that the proposed flowsheet is a feasible method for separating neptunium and uranium from sulfates, thorium, and other metal impurities. The proposed flowsheet calls for stripping the sulfates, thorium, and other metal impurities into the 1AW stream and extracting and then stripping the neptunium and uranium into the 1BP stream. SASSE predicts that separation of thorium from the other actinides can be accomplished with actinide losses of 0.01% or less. It is assumed that other metal impurities such as iron, aluminum, and fission products will follow the thorium into 1AW. Due to an organic/aqueous distribution coefficient that is close to one, SASSE predicts that plutonium(VI) (Pu(VI)) is split between the A Bank and B Bank aqueous output streams, with 27% going to 1AW and 73% going to 1BP. An extrapolated distribution coefficient based on unvalidated Ce(IV) distribution measurements at a single nitrate concentration and a comparison with thorium(IV) (Th(IV)) distributions indicates that Ce(IV) could reflux in 1B Bank. If the Ce(IV) distribution coefficient is lower than would be predicted by this single point extrapolation, but still higher than the distribution coefficient for Th(IV), then Ce(IV) would follow Np(VI) and uranium(VI) (U(VI)) into 1BP. The SASSE model was validated using data from a 1964 oxidizing flowsheet for the recovery of Np(VI) in Second Cycle. For the proposed flowsheet to be effective in recovering neptunium, the addition of approximately 0.025 M ceric ammonium nitrate (Ce(NH4)2(NO3)6) to both the 1AF and 1AS streams is required to stabilize the neptunium in the +6 oxidation state. The cerium added to 1AF and 1AS must remain in the +4 oxidation state to stabilize Np(VI).},
doi = {10.2172/1183724},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sat Apr 01 00:00:00 EST 2006},
month = {Sat Apr 01 00:00:00 EST 2006}
}

Technical Report:

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  • A flowsheet has been proposed to separate neptunium from solutions in H-Canyon Tanks 16.4, 12.5, and 11.7 in the First Cycle solvent extraction banks, in which cerium(IV) (Ce(IV)) serves as an agent to oxidize neptunium to neptunium(VI) (Np(VI)). A SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) spreadsheet model indicates that the proposed flowsheet is a feasible method for separating neptunium and uranium from sulfates, thorium, and other metal impurities. The proposed flowsheet calls for stripping the sulfates, thorium, and other metal impurities into the 1AW stream and extracting and then stripping the neptunium and uranium into the 1BP stream. SASSEmore » predicts that separation of thorium from the other actinides can be accomplished with actinide losses of 0.01% or less. It is assumed that other metal impurities such as iron, aluminum, and fission products will follow the thorium into 1AW. Due to an organic/aqueous distribution coefficient that is close to one, SASSE predicts that plutonium(VI) (Pu(VI)) is split between the A Bank and B Bank aqueous output streams, with 27% going to 1AW and 73% going to 1BP. An extrapolated distribution coefficient based on unvalidated Ce(IV) distribution measurements at a single nitrate concentration and a comparison with thorium(IV) (Th(IV)) distributions indicates that Ce(IV) could reflux in 1B Bank. If the Ce(IV) distribution coefficient is lower than would be predicted by this single point extrapolation, but still higher than the distribution coefficient for Th(IV), then Ce(IV) would follow Np(VI) and uranium(VI) (U(VI)) into 1BP. The SASSE model was validated using data from a 1964 oxidizing flowsheet for the recovery of Np(VI) in Second Cycle. For the proposed flowsheet to be effective in recovering neptunium, the addition of approximately 0.025 M ceric ammonium nitrate (Ce(NH 4) 2(NO 3) 6) to both the 1AF and 1AS streams is required to stabilize the neptunium in the +6 oxidation state. The cerium added to 1AF and 1AS must remain in the +4 oxidation state to stabilize Np(VI).« less
  • H-Canyon Engineering (HCE) is evaluating the feasibility of processing material from the Super Kukla Prompt Burst Reactor, which operated at the Nevada Test Site from 1964 to 1978. This material is comprised of 90 wt % uranium (U) (at approximately 20% 235U enrichment) alloyed with 10 wt % molybdenum (Mo). The objective is to dissolve the material in nitric acid (HNO{sub 3}) in the H-Canyon dissolvers and then to process the dissolved material through H-Canyon First and Second Cycle solvent extraction. The U product from Second Cycle will be sent to the highly enriched uranium (HEU) blend down program. Inmore » the blend down program, enriched U from the 1EU product stream will be blended with natural U at a ratio of 1 part enriched U per 3.5 parts natural U to meet a reactor fuel specification of 4.95% 235U before being shipped for use by the Tennessee Valley Authority (TVA) in its nuclear plants. The TVA specification calls for <200 mg Mo/g U (200 ppm). Since natural U has about 10 mg Mo/g U, the required purity of the 1EU product prior to blending is about 800 mg Mo/g U, allowing for uncertainties. HCE requested that the Savannah River National Laboratory (SRNL) define a flowsheet for the safe and efficient processing of the U-10Mo material. This report presents a computational model of the solvent extraction portion of the proposed flowsheet. The two main objectives of the computational model are to demonstrate that the Mo impurity requirement can be met and to show that the solvent feed rates in the proposed flowsheet, in particular to 1A and 1D Banks, are adequate to prevent refluxing of U and thereby ensure nuclear criticality safety. SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction), a Microsoft Excel spreadsheet that supports Argonne National Laboratory's proprietary AMUSE (Argonne Model for Universal Solvent Extraction) code, was selected to model the U/Mo separation flowsheet. SASSE spreadsheet models of H-Canyon First and Second Cycle solvent extraction show that a standard unirradiated fuel flowsheet is capable of separating U from Mo in dissolved solutions of a U/Mo alloy. The standard unirradiated fuel flowsheet is used, except for increases in solvent feed rates to prevent U refluxing and thereby ensure nuclear criticality safety and substitution of higher HNO{sub 3} concentrations for aluminum nitrate (Al(NO{sub 3})){sub 3} in the feed to 1A Bank. (Unlike Savanah River Site (SRS) fuels, the U/Mo material contains no aluminum (Al). As a result, higher HNO3 concentrations are required in the 1AF to provide the necessary salting.) The TVA limit for the final blended product is 200 {micro}g Mo/g U, which translates to approximately 800 mg Mo/g U for the Second Cycle product solution. SASSE calculations give a Mo impurity level of 4 {micro}g Mo/g U in the Second Cycle product solution, conservatively based on Mo organic-to-aqueous distributions measured during minibank testing for previous processing of Piqua reactor fuel. The calculated impurity level is slightly more than two orders of magnitude lower than the required level. The Piqua feed solution contained a significant concentration of Al(NO{sub 3}){sub 3}, which is not present in the feed solution for the proposed flowsheet. Measured distribution data indicate that, without Al(NO{sub 3}){sub 3} or other salting agents present, Mo extracts into the organic phase to a much lesser extent, so that the overall U/Mo separation is better and the Mo impurities in the Second Cycle product drop to negligible concentrations. The 1DF U concentration of 20 g/L specified by the proposed flowsheet requires an increased 1DX organic feed rate to satisfy H-Canyon Double Contingency Analysis (DCA) guidelines for the prevention of U refluxing. The ranges for the 1AX, 1BS, and 1DX organic flow rates in the proposed flowsheet are set so that the limiting ratios of organic/aqueous flow rates exactly meet the minimum values specified by the DCA.« less
  • A method is described for the separation and determination of neptunium in urarnium--fission product -mixtures. A two-cycle extraction system is used. Neptunium is oxidized to +6 with permangarate and quantitatively extracted as a nitrate complex into methyl isobutyl ketone from an acid deficient aluminum nitrate salting solution containing tetrapropyl ammonium nitrate. Neptunium is stripped from the ketone phase and simultaneously reduced to +4 by contact with ferrous chloride-hydroxylamine solution, then quantitutively extracted into thenoyltrifluoroacetone-xylene. The extraction of uranium and plutonium is less than 0.1% and 0.01%, respectively. Rutherium and zircorium, the only 80day cooled fission products which follow the neptunium,more » are decontaminated to greater than 1 x 10/sup 4/. (auth)« less